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Trans. Nonferrous Met. Soc.

China 25(2015) 3436−3441

Comprehensive ecological risk assessment for

heavy metal pollutions in three phases in rivers

Ying ZHANG1, Jun ZHOU1,2, Feng-jie GAO1, Bao-jie ZHANG2, Biao MA2, Li-qing LI3
1. College of Resources and Environment, Northeast Agricultural University, Harbin 150030, China;
2. Heilongjiang Research Academy of Environmental Science, Harbin 150056, China;
3. School of Energy Science and Engineering, Central South University, Changsha 410083, China
Received 27 November 2014; accepted 10 March 2015

Abstract: Literature lacked in providing a comprehensive research on heavy metal detection in aquatic, biological and sedimentary
states of rivers. The present study was imparted with all these three components of the river. Heavy metal toxicity or pollution index
was used as a tool for ecological risk assessment by considering the single state studies conducted by many researchers. An intensive
ecological risk assessment model was constructed and heavy metals were indicated as a serious threat to the environment. The model
was applied to determining five toxic heavy metals in three states of the Songhua River. According to the ecological risk index, heavy
metal pollution in three phases was categorized as aquatic>biological>sedimentary, while the overall descending order of heavy
metal ecological risk index was as Cd>Hg>As>Pb>Cr. Cd and Hg were selected as the priority pollutants of Songhua River.
Key words: comprehensive ecological risk assessment; priority pollutants selection; heavy metal; Songhua River

environment [4]. Ten fish species were collected from

1 Introduction Bangshi River at Savar in Bangladesh in two different
seasons to measure eight heavy metals (Pb, Cd, Ni, Cr,
An increase in industrial production and Cu, Zn, Mn, and As) [5]. The water quality index was
urbanization was believed responsible for increasing implemented for heavy metals risk assessment and water
concentration of heavy metals into the natural quality characterization of River Soan, Pakistan [6].
environment, not only posing serious threat to However, most of the researchers detected heavy metals
individuals and species but also causing a negative effect in single medium only. No intensive research on heavy
on the ecological system. Excessive amount of heavy metal pollution in all aquatic, biological and sedimentary
metals resulted in severe impacts on human body, such phases of the river was reported. Although many studies
as acute and chronic intoxication, cancer, teratogenesis, investigated screening methods for priority pollutants in
and mutations [1]. Currently, heavy metal contamination aqueous environments, most of them focused on heavy
got great attention by researchers due to its potential metal contamination of organic matters causing great
hazard to environmental pollution locally and globally threat to human body [7]. This was a problem to
[2]. Different methods were adopted and implemented to formulate a scientific evaluation model for determination
calculate an ecological risk assessment of heavy metals of heavy metals as priority pollutants for intensive
in Xiawan Port sediments like potential ecological risk research on target rivers due to the demand of high
index (RI), risk assessment code (RAC) by modifying an standard heavy metal detection devices and operators. By
index, modified potential ecological risk index (MRI) [3]. considering heavy metal pollution assessment models
Four different methods, named mineralogical analysis, [8−10] and priority pollutant screening methods [11−13]
three-stage BCR sequential extraction procedure, adopted and observed in different researches, the
dynamic leaching test and Hakanson potential ecological present study opted relevant indexes to construct
risk index method were used to evaluate the zinc residual a comprehensive ecological risk assessment model
leaching and its potential ecological risks on to detect heavy metals in aqueous, biological and

Foundation item: Project (2010467038) supported by the Special Fund for Environmental Research in the Public Interest, China
Corresponding authors: Bao-jie ZHANG; Tel: +86-451-51970502; E-mail:;
Jun ZHOU; Tel: +86-451-5197516; E-mail:
DOI: 10.1016/S1003-6326(15)63979-6
Ying ZHANG, et al/Trans. Nonferrous Met. Soc. China 25(2015) 3436−3441 3437
sedimentary phases. Heavy metals with higher ecological
risks were selected as the priority pollutants to control
heavy metal pollution in rivers.

2 Migration and transmission of heavy

metals among three phases in rivers

Heavy metals after entering in any environmental

component were easily transmitted and accumulated in
food chains [14], same in the case of water bodies, heavy
metals eventually entered in human bodies by edible
marine food like fish [15]. This process not only Fig. 1 Simulation of migration and transmission process of
poisoned the fish, but also caused the alarming situation heavy metals in river ecosystem
towards humans. Moreover, heavy metals in water
bodies showed a tendency to react with organic literature, in the current study, toxicity coefficient,
polymers, forming a complex or chelate by adhering to pollution index, and detection rate were selected as the
surface of clay minerals. These pollutants were key factors to construct the risk assessment model to
ultimately settled and accumulated in sediments and detect heavy metals in rivers.
acted as secondary pollutants in water bodies by 3.1.1 Toxicity coefficient of heavy metals (Tri)
undergoing a series of physical, chemical and biological Toxicity coefficient Tri represented the toxicity level
processes [16]. The migration and transmission process and the biological sensitivity for heavy metals. Toxicity
of heavy metals in river ecosystem is shown in Fig. 1. coefficients commonly used are shown in Table 2.
3.1.2 Pollution index of heavy metals (Cfi)
3 Construction of risk evaluation model for Pollution index Cfi represented the richness and
heavy metals in three phases in rivers pollution degree of a single heavy metal, which was
denoted in Eq. (1):
3.1 Construction of index system
Cfi = C i /Cni (1)
Table 1 shows the major assessment models for
heavy metal pollutions locally and globally. Heavy where Ci is the detected value of a single heavy metal
metals pollution in rivers were mainly influenced by (mg/kg); Cni is the background value (mg/kg).
biological toxicity, absorption and contamination extent. 3.1.3 Detection rate of heavy metals (Fsi)
By keeping in view the model construction concepts in Detection rate Fsi symbolized the pollution scale and

Table 1 Main models of heavy metal pollution assessment

Model name Formula Indication

Cn Cn represents the content of element n in sediments;

Index of geo- I geo = log 2 Bn refers to the background value of n in
accumulation [8] kBn
sedimentary rock (regular rock).
CFi = Ci is the detected content of element i; Coi is
Pollution load the background value of i; PLI is the pollution
index [17] PLI = n CF1 × CF2 × ⋅ ⋅ ⋅ × CFn bearing coefficient of a certain point; PLIzone is
the pollution bearing coefficient of a certain region.
PLI zone = n PLI1 × PLI 2 × ⋅ ⋅ ⋅ × PLIn

Cdi Cdi is the detected concentration of pollutants in sediments;
Potential ecological risk
RI = ∑ Tri × Cri is the background value of pollutants in sediments;
index [9] i Cri i
Tr refers to the toxicity coefficient of single factor pollutant.

Es is the total concentration of heavy metals; ED is the

Excess after regression ERA( B) = [ Es − ( βCMg + α )] / ED , background concentration; CMg refers to the Mg concentration;
analysis [10] ERA( A) = ( Es − ED ) / ED β represents the regression slope between heavy metals and Mg;
α is the regression intercept between heavy metals and Mg.

SE indicates the heavy metal content in sediments; SAl is the Al

Sediment enrichment
K SEF = ( s E / s Al − aE / aAl ) /(aE / aAl ) content in sediments; aE is the content of heavy metals in
factor [18] unpolluted sediments; aAl is Al content in unpolluted sediments.
3438 Ying ZHANG, et al/Trans. Nonferrous Met. Soc. China 25(2015) 3436−3441
Table 2 Toxicity coefficients of different heavy metals arithmetic weight of each heavy metal in various water
Heavy metal Tri components a, b and c to measure the heavy metal
Hg 40 weight in aquatic, biological and sedimentary phases ζ, η,
θ, respectively (Eq. (3)). Table 3 shows the heavy metals
Cd 30
weights in three phases in rivers.
Cr 2
a a a
As 10 ζ = ;η= ;θ= (3)
a+b+c a+b+c a+b+c
Pb 5
Cu 5
Zn 1 α1 A + β1B + γ 1C + δ1D + ε1E
a= ,
Ni 2
A+ B +C + D + E

Mn 2 α 2 A + β 2 B + γ 2C + δ 2 D + ε 2 E
b= ,
A+ B +C + D + E

detection rate of a single heavy metal, which was shown α 3 A + β 3 B + γ 3C + δ 3 D + ε 3 E

c= .
in Eq. (2): A+ B +C + D + E

Fsi = S i / S ti (2)
3.2.2 Weight value determination
where Si is the number of sections that detected a single The analytic hierarchy process was adopted to
heavy metal; Sti indicates the total number of detection determine the weight coefficient. This section referred to
sections. the concentration comparison method for a single heavy
metal in different water environments to construct a
3.2 Weight of indexes verification matrix as described in Surface Water Quality
3.2.1 Weight determination Assessment Standard GB3838—2002. Six experts were
The weight determination method of heavy metals invited to construct the verification matrix for I−V water
(ζ, η, θ) in the three phases was as follows: 1) Heavy quality in aquatic, biological and sedimentary phases.
metals weight determination coefficients in aquatic, The common conclusion of their researches was adopted
biological and sedimentary phases were x, y and z, to construct the weight coefficient matrix, as shown in
respectively; 2) Dividing water environment according to Table 4.
water qualities into I−V categories, and weight
coefficients for these categories were α, β, γ, δ and ε, 3.3 Comprehensive ecological risk index in three-
respectively; 3) Heavy metal weight coefficients x, y and phases in rivers
z were multiplied with α, β, γ, δ and ε to obtain the By considering the evaluation indexes in literature,
weight coefficient of each heavy metal in every the ecological risk indexes were established to detect
selected phase of water bodies, αi, βi, γi, δi and εi; heavy metals in aquatic, biological, and sedimentary
4) Determination of the number of different water quality phases (represented by W, F and S, Eq. (4)). Heavy
categories A, B, C, D and E; 5) Calculation of the mean metal impact on human was varied depending upon their

Table 3 Weight distribution of heavy metals in three phases in rivers

Water quality category
Three phase I(α) II(β) III(γ) IV(δ) V(ε)
Weight index No. Weight index No. Weight index No. Weight index No. Weight index No.
Aquatic (x) α1 A β1 B γ1 C δ1 D ε1 E ζ
Biological (y) α2 A β2 B γ2 C δ2 D ε2 E η
Sedimentary (z) α3 A β3 B γ3 C δ3 D ε3 E θ

Table 4 Weight coefficient of different heavy metals in rivers

Three Weight coefficients in different water quality environments
phase α (0.363) β (0.276) γ (0.182) δ (0.117) ε (0.062)
Aquatic (0.625) 0.227 0.173 0.114 0.073 0.039
Biological (0.239) 0.087 0.066 0.043 0.028 0.015
Sedimentary (0.137) 0.050 0.038 0.025 0.016 0.008
Ying ZHANG, et al/Trans. Nonferrous Met. Soc. China 25(2015) 3436−3441 3439
accumulation in different phases, consequently, different Province Surface Water Function Regions DB22/388—
risk weights were assigned to the heavy metals in 2004 and Heilongjiang Province Surface Water
different phases. Comprehensive ecological risk index R Environment Regionalization and Water Quality
was obtained in Eq. (5) and heavy metals with the higher Supplementary Standards DB23/485—1998. Shaokou to
R values were selected as the priority pollutants in Tongjiang section was selected as the research target and
rivers. it was divided into 11 water sampling areas, whereas, 1
section was followed under category II, 7 in category III
W ( F or S ) = Tri × Cfi × Fsi (4)
and 3 in category IV. The calculation process of weight
R = ζW + ηF + θS (5) values was as follows, such as Hg.
0.173 × 1 + 0.114 × 7 + 0.073 × 3
4 Model application and verification a= = 0.108
1+ 7 + 3

4.1 Model application 0.066 × 1 + 0.043 × 7 + 0.028 × 3

b= = 0.041
4.1.1 Research region selection and data collection 1+ 7 + 3
The model was applied to the third largest river in 0.038 × 1 + 0.025 × 7 + 0.016 × 3
China named Songhua River. Songhua River was c= = 0.024
1+ 7 + 3
connected to Nen River on the north and the Second
Songhua River on the south. The two branches were ζ = = 0.624
0.108 + 0.041 + 0.024
merged into the mainstream of Songhua River at Sancha
River and joined Heilongjiang River at Tongjiang City, η= = 0.237
having great impacts on the water quality of 0.108 + 0.041 + 0.024
Heilongjiang River. Five main control pollutants Hg, Cd, 0.024
Cr, As and Pb were selected as research objects and the
θ= = 0.139
0.108 + 0.041 + 0.024
samples were collected from the Second Songhua River
and trunk stream of Songhua River from May 2011 to The results of ecological risk assessment of heavy
May 2012. metals in Songhua River are show in Table 5 and Fig. 3.
The water samples were collected from 10 sections Table 5 and Fig. 3 explained that: 1) The biological
for 8 times. Overall 88 fish samples were collected from toxicity of the five types of heavy metals in Songhua
5 sections for once, including catfish (sarcophagous), River were different with toxicity coefficient in a
carp and crucian (omnivory), chub (herbivore). One descending order of Hg>Cd>As>Pb>Cr, Cfi showed that
sediment sample was collected from each of 8 selected the richness of heavy metals in the three phases was as
sections. The background information of fish samples
was assembled from Ref. [19], 16 water samples and 23 Table 5 Comprehensive ecological risk assessment of heavy
sediment samples were collected from six rivers in May metals in Songhua River
2011 (Fig. 2). All samples were detected by ICP-MS. Three Heavy i
T Cfi Fsi W, F, S ξ, η, θ R
phase metal r
Water 1.40 0.34 19.04 0.62
Fish Hg 40 1.30 1 52.00 0.24 28.48
Sediment 0.75 1 30.00 0.14
Water 1.30 1 39.00 0.62
Fish Cd 30 1.17 1 35.10 0.24 37.64
Sediment 1.20 1 36.00 0.14
Water 5.11 0.76 7.77 0.62
Fish Cr 2 1.13 1 2.26 0.24 5.67
Sediment 1.10 1 2.20 0.14
Water 2.34 1 23.40 0.62
Fish As 10 1.33 1 13.30 0.24 19.14
Fig. 2 Spatial distribution of sampling sections Sediment 1.03 1 10.30 0.14
Water 3.37 0.50 8.43 0.62
4.1.2 Model calculation and results analysis
Fish Pb 5 1.25 1 6.25 0.24 7.41
The target river was segmented according to water
Sediment 0.98 1 4.90 0.14
quality classification standards prescribed in Jilin
3440 Ying ZHANG, et al/Trans. Nonferrous Met. Soc. China 25(2015) 3436−3441
the significance of this model.

4.3 Model discussion

Toxicity coefficient and heavy metal concentration
were the most important indexes for most models (Table
1). By analyzing the model construction and selection
methods of priority pollutants in foreign studies, the
comprehensive ecological risk assessment model was
constructed. The results illustrated that heavy metals
with higher toxicity coefficient have higher
comprehensive ecological risk index (R and Tr have
significant correlation), but lacked in direct correlation
due to the influence of pollutant concentration,
Fig. 3 Ecological risk index of heavy metals in three phases in background value and detection rate. For example,
Songhua River Tr(Cd)<Tr(Hg), but R(Cd)>R(Hg). The low detection rate
of Hg in aquatic phase also decreased the ecological risk
aquatic>biological>sedimentary, Fsi represented a higher index of Hg in biological and sedimentary phases, while
detection rate of heavy metals; 2) The detection rate of an ecological risk index of the Cd was calculated higher.
Hg, Cr, and Pb in aquatic phase was less than 1, but the Therefore, the detection rate was considered as an
pollution index was marked up to 1.40, 5.11 and 3.37, important influencing factor for comprehensive effects.
respectively, this phenomenon indicated the uneven This model was designed to screen out the priority heavy
spatial distribution of these three kinds of heavy metals, metal pollutants from rivers by adopting comprehensive
mainly higher values were detected in aquatic phase, the ecological risk indexes. It was not only time and cost
pollution index of Hg and Pb in sediments was smaller efficient, but also helpful for actual heavy metal
than 1, but the detection rate was 100%, this was due to assessment and transformation in the rivers. In addition,
their high background values; 3) The ecological risk this work probed the integrated ecological risk of five
index of Hg in biological phase was the highest (52), types of toxic heavy metals, and was only applied in the
greater than the sum of risk indexes in water and solid case study of Songhua River, but further researches on
phases (49), the ecological risk of Cd was similar in three more heavy metals and rivers were needed to explain the
phases, while the other 3 heavy metals in an descending specifications of the application.
order was water>biological>solid; 4) The comprehensive
ecological risk index (R) descending order of five heavy 5 Conclusions and prospects
metals was Cd(37.64)>Hg(28.48)> As(19.14)>Pb(7.41)>
Cr(5.67), and Cd and Hg were selected as priority 1) Heavy metal toxicity coefficient, pollution index
pollutants in Songhua River. and detection rate were selected as the key factors to
calculate the ecological risk index in aquatic, biological
4.2 Model verification and sedimentary phases. Different parameters such as
ZHU and WANG [20] reviewed about 51 papers sampling numbers, water quality and pollutant
consisted of 34478 samples from seven major Chinese concentrations were selected for absolute study of three
water systems at different time. According to the heavy phases. Finally, the comprehensive ecological risk
metal characteristics analysis, Songhua River was ranked assessment model was constructed and heavy metals of
third on ecological risk, following Pearl River and Haihe higher risk indexes were concluded as priority pollutants.
River. The ecological risk of Hg was higher than that of 2) The model was applied to assessing five types of
Cd. SUN et al [21] reported higher concentrations of Cd toxic heavy metals in the Songhua River. The results
in fish of the Second Songhua River than that of the concluded higher detection rate of heavy metals and
trunk stream Songhua River, while Hg concentration in descending order of their biological toxicity was as
fish was found higher in the trunk stream of the Songhua Hg>Cd>As>Pb>Cr, while the richness in phases was
River. LU et al [22] investigated the higher ecological categorized as aquatic> biological> sedimentary.
risk index of Hg and Cd in sediment samples collected 3) The ecological risk index of five heavy metals in
from middle and lower stream of the Second Songhua the single medium was as aquatic>biological>
River. The research evidenced the Hg and Cd as the sedimentary, while the comprehensive ecological risk
greatest ecological risk to water, fish and sediments of index in three phases was Cd>Hg>As>Pb>Cr. Therefore,
the Songhua River. These researches were consistent Cd and Hg were selected as the priority pollutants of the
with the results of the present study, which demonstrated Songhua River.
Ying ZHANG, et al/Trans. Nonferrous Met. Soc. China 25(2015) 3436−3441 3441
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张 颖 1,周 军 1,2,高凤杰 1,张宝杰 2,马 彪 2,李立清 3

1. 东北农业大学 资源与环境学院,哈尔滨 150030;2. 黑龙江省环境科学研究院,哈尔滨 150056;

3. 中南大学 能源科学与工程学院,长沙 410083

摘 要:当前,有关重金属在河流水相、生物相和固相三相空间的综合污染效应研究尚未见报道,因此主要围绕
数和污染指数。本文构建的综合生态风险评价模型表明重金属对环境安全具有严重威胁。该模型应用于松花江 5
种有毒重金属污染综合效应评价,结果表明,5 种有毒重金属在单一介质中生态风险指数均表现为水相>生物相>
固相,三相空间综合生态风险指数由高到低排序为 Cd>Hg>As>Pb>Cr。在此基础上,将 Cd 和 Hg 筛选为松花江
(Edited by Yun-bin HE)